Development of complexes with a Multiple Bond between Transition Metal and Phosphor us

过渡金属和磷之间具有多重键的配合物的开发

• 批准号: 10440195
• 负责人: MIYOSHI Katsuhiko
• 金额: $ 8.58万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10440195/
• 关键词: Phosphenium Complex; Phosphide Complex; Double Bond; Migration Reaction; Stannylene Complex; One Electron Reduction; OR引き抜き反応; タングステン錯体

The reaction of [Cp(CO)ィイD22ィエD2(SnィイD1nィエD1BuィイD23ィエD2)W{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe(OMe)}] with a Lewis acid revealed the formation of a phosphenium complex, followed by migration of a ィイD1nィエD1BU group from Sn to P to give a stannylene complex. If the reaction takes place in the presence of NaBPhィイD24ィエD2, a phosphi de complex, Cp(CO)ィイD22ィエD2W{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe} is formed. This unprecedented reaction is considered to be a W-P bond order increment by one with elimination of a stannyl and a methoxy group. The reaction proceeds with one electron reducti on of a phosphenium complex by NaBPh4, followed by stannyl radical elimination.The reaction of a Lewis acid with a ruthenium complex, [Cp(CO)(ERィイD23ィエD2)Ru-{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe(OMe)}] (where E = C, Si , Ge, Sn), which has both diamino-substituted phosphite and a group 14 element ligand was examined. Irrespective of the kind of E, an OMe group on the phosphorus is abstracted as an anion to give a phosphenium complex. The following reaction depends on the kind of E. If ERィイD23ィエD2 is an alkyl group, the ligand migrates from Ru to the phospheni um phosphorus, whereas if ERィイD23ィエD2 is a silyl or a germyl group, no migration reaction takes place. If ERィイD23ィエD2 is a stannyl group, an al kyl group on the tin migrates to the phosphenium phosphorus to give a stannylene complex, which has a double bond between Ru and Sn.The reaction of a Lewis acid with [Cp(CO)(SiMeィイD22ィエD2OMe)Fe{PN(Me)CHィイD22ィエD2CHィイD22ィエD2-NMe(OMe)}] containing an OR group on both coordinating P and Si atoms revealed that selective OR abstraction from Si occurs to give a silylene complex.

[CP（CO）D22E D2（Sn至P以产生Stannylene复合物）的反应。如果在存在Nabphy D24E D2的情况下发生反应，磷酸化合物（CO）II D22IE D2W {Pn（Me）Chii D22IE D22IE D22IE D2NME be be be be be be be be be be be be be be exend。随着stannyl的发射和方法组的发射。 C，Si，GE，SN）具有二氨基溶剂的磷酸盐和14组元素配体，无论e的E种类，磷上的OME群都被抽出作为磷酸化的磷酸元素的。磷，而如果ERI D23E D2是Stannyl群，则锡的Al kyl基团迁移到磷磷磷磷磷酸磷酸磷酸化合物中，它具有ru和sn之间的双键。 D2-NME（OME）}]在配位P和SI原子上包含或组均表明SI的选择性或抽象发生以给出甲硅烷基络合物。

项目成果

Hiroshi Nakazawa: "Syntheses,Structure,and Berry Pseudorotatin of Ruthenium-Phosphorane Complexes"Organometallics. 18. 2961-2969 (1999)

Hiroshi Nakazawa：“钌-磷烷配合物的合成、结构和贝里假旋转”有机金属化合物。

Katsuhiko Miyoshi: "Selective Abstraction of an OR Group in the Reaction of(C_5H_5)(CO)Fe{SiMe_2(OR)}{PN(Me)CH_2CH_2NMe(OR^2)}with a Lewis Acid:Preferential Formation of a Silylene Complex over a Phosphenium, Complex" Organometallics. (accepted).

Katsuhiko Miyoshi：“(C_5H_5)(CO)Fe{SiMe_2(OR)}{PN(Me)CH_2CH_2NMe(OR^2)}与路易斯酸反应中OR基团的选择性抽象：优先形成硅烯络合物

Kazumori Kawamura: "Selective Abstraction of an OR Group in the Reaction of (CィイD25ィエD2HィイD25ィエD2) (CO)Fe{SiMeィイD22ィエD2(ORィイD11ィエD1)}{PN(Me)CHィイD22ィエD2CHィイD22ィエD2NMe(ORィイD12ィエD1)} with a Lewis Acids: Preferential Formation of a Silylene Complex over a Pho

Kazumori Kawamura：“(C-D25-D2H-D25-D2) (CO)Fe{SiMe-D22-D2 (OR-D11-D1) }{PN(Me)CHD22D2CHD22D2NMe( ORD12D1)} 与路易斯酸：相对于 Pho 优先形成亚硅基络合物

Kazumori Kawamura: "Reaction of Ruthenium Complexes Having Both a Phosphite and a Group 14 Element Ligand with a Lewis Acid"Organimetallics. 18. 4785-5794 (1999)

Kazumori Kawamura：“具有亚磷酸酯和第 14 族元素配体的钌配合物与路易斯酸的反应”有机金属。

Hiroshi Nakazawa: "Reactivity of a Catiotic Phosphenium Complex of Tungsten Containing Aklyl or a Stannyl Group"Phosphorus,Sulfur,and Silicon. 144. 45-48 (1999)

Hiroshi Nakazawa：“含烷基或甲锡烷基的钨的阳离子磷锍配合物的反应性”磷、硫和硅。